M. Das, D.F. O’Shea / Tetrahedron xxx (2013) 1e13
11
diethyl ether (10ꢂ3 mL), the organic layer washed with water
(10 mL), brine (10 mL), dried over sodium sulfate, and concentrated
to dryness. Purification by silica gel chromatography eluting with
cyclohexane/ethyl acetate (96:4) yielded a colorless oil (65.6 mg,
J¼1.9 Hz, 1H), 6.98 (dd, J¼8.2, 1.9 Hz, 1H), 6.88 (d, J¼8.2 Hz, 1H), 5.51
(dd, J¼12.0, 3.1 Hz, 1H), 3.91 (s, 3H), 3.90 (s, 3H), 3.36 (dd, J¼16.4,
12.0 Hz, 1H), 3.11 (dd, J¼16.4, 3.1 Hz, 1H) ppm. 13C NMR (100 MHz,
CDCl3):
d 165.6, 149.5, 149.4, 139.2, 134.0, 131.3, 130.6, 128.0, 127.5,
75%). 1H NMR (400 MHz, CDCl3):
d
7.39e7.29 (m, 6H), 7.28e7.23 (m,
125.3, 118.9, 111.2, 109.6, 80.1, 56.2, 56.1, 35.8 ppm. HRMSeESI
1H), 6.84 (d, J¼8.4 Hz, 2H), 3.07 (d, J¼13.4 Hz, 1H), 2.98 (d,
[MþH]þ: 285.1125, C17H17O4 requires 285.1127.
J¼13.4 Hz, 1H), 1.69 (br s, 1H), 1.57 (s, 3H) ppm. 13C NMR (100 MHz,
CDCl3):
d
147.2, 136.0, 132.4, 131.2, 128.3, 127.0, 125.1, 120.8, 74.6,
4.41. 3-(5-Methylfuran-2-yl)isochroman-1-one, 8c
79
50.0, 29.5 ppm. HRMSeESI [MꢁOH]þ: 273.0278, C15
H Br requires
14
273.0279.
A solution of 2-((trimethylsilyl)methyl)benzoic acid, 3b (104 mg,
ꢀ
0.50 mmol), 5-methylfurfural (60
m
L, 0.60 mmol), and 4 A MS
4.38. 1-(4-Bromophenyl)-4-phenylbutan-2-ol, 6l
(100 mg) in anhydrous DMF (2.0 mL) was treated with CsF
(152.0 mg, 1.0 mmol) under N2 and the resulting solution was
stirred at 80 ꢀC for 6 h. The reaction mixture was cooled to rt, 2 M
HCl (20 mL) was added and stirred for another 1 h. The residue was
extracted with ethyl acetate (20ꢂ3 mL), the organic layer washed
with water (2ꢂ10 mL), brine (10 mL), dried over sodium sulfate, and
concentrated to dryness. Purification by silica gel chromatography
eluting with cyclohexane/ethyl acetate (90:10) yielded a brown
crystalline solid, mp 73e75 ꢀC (85.5 mg, 75%). 1H NMR (400 MHz,
A solution of (4-bromobenzyl)trimethylsilane, 3h (145.8 mg,
0.60 mmol) and 3-phenylpropionaldehyde (40 L, 0.3 mmol) in
m
anhydrous THF (1.2 mL) was treated with TBAT (32.4 mg,
0.06 mmol) and the resulting solution was stirred under N2 at
reflux for 6 h. The reaction mixture was cooled to rt, solvent re-
moved under reduced pressure, and 2 M HCl (10 mL) was added.
The residue was extracted with diethyl ether (10ꢂ3 mL), the or-
ganic layer washed with water (10 mL), brine (10 mL), dried over
sodium sulfate, and concentrated to dryness. Purification by silica
gel chromatography eluting with cyclohexane/ethyl acetate (98:2)
yielded a colorless solid, mp 67e69 ꢀC (59.6 mg, 65%). 1H NMR
CDCl3):
d
8.12 (d, J¼7.5 Hz, 1H), 7.57 (td, J¼7.5, 1.2 Hz, 1H), 7.42 (t,
J¼7.5 Hz, 1H), 7.30 (d, J¼7.5 Hz, 1H), 6.28 (d, J¼3.1 Hz, 1H), 5.95 (d,
J¼3.1 Hz, 1H), 5.53 (dd, J¼11.2, 3.4 Hz, 1H), 3.57 (dd, J¼16.4, 11.2 Hz,
1H), 3.18 (dd, J¼16.4, 3.4 Hz, 1H), 2.30 (s, 3H) ppm. 13C NMR
(400 MHz, CDCl3):
d
7.41 (d, J¼8.3 Hz, 2H), 7.30e7.23 (m, 2H),
(100 MHz, CDCl3): d 165.0, 153.3, 149.0, 138.8, 134.0, 130.6, 128.0,
7.21e7.14 (m, 3H), 7.06 (d, J¼8.3 Hz, 2H), 3.84e3.75 (m, 1H),
127.6, 125.1, 110.1, 106.6, 73.3, 31.6, 13.7 ppm. HRMSeESI [MþNa]þ:
2.87e2.60 (m, 4H), 1.89e1.73 (m, 2H), 1.50 (br s, 1H) ppm. 13C NMR
251.0683, C14H12O3Na requires 251.0684.
(100 MHz, CDCl3):
d 141.9, 137.5, 131.7, 131.3, 128.6, 128.6, 126.1,
120.5, 71.9, 43.6, 38.6, 32.2 ppm. HRMSeESI [MþNa]þ: 327.0367,
4.42. 3-(5-Methylthiophen-2-yl)isochroman-1-one, 8d
C
16H17ONa79Br requires 327.0360.
A solution of 2-((trimethylsilyl)methyl)benzoic acid, 3b (104 mg,
4.39. 3-Phenylisochroman-1-one, 8a28
solution of 2-((trimethylsilyl)methyl)benzoic acid, 3b
0.50 mmol), 5-methylthiophene-2-carbaldehyde (65 mL, 0.60 mmol),
ꢀ
and 4 A MS (100 mg) in anhydrous DMF (2.0 mL) was treated with
CsF (152.0 mg, 1.0 mmol) under N2 and the resulting solution was
stirred at 80 ꢀC for 6 h. The reaction mixture was cooled to rt, 2 M
HCl (20 mL) was added and stirred for another 1 h. The residue was
extracted with ethyl acetate (20ꢂ3 mL), the organic layer was
washed with water (2ꢂ10 mL), brine (10 mL), dried over sodium
sulfate, and concentrated to dryness. Purification by silica gel chro-
matography eluting with cyclohexane/ethyl acetate (98:2) yielded
A
ꢀ
(41.6 mg, 0.20 mmol) and benzaldehyde (25 mL, 0.24 mmol), and 4 A
MS (50 mg) in anhydrous DMF (0.8 mL) was treated with CsF
(58.4 mg, 0.40 mmol) under N2 and the resulting solution was
stirred at 80 ꢀC for 6 h. The reaction mixture was cooled to rt, 2 M
HCl (10 mL) was added and stirred for another 30 min. The residue
was extracted with ethyl acetate (10ꢂ3 mL), the organic layer
washed with water (2ꢂ10 mL), brine (10 mL), dried over sodium
sulfate, and concentrated to dryness. Purification by silica gel
chromatography eluting with cyclohexane/ethyl acetate (90:10)
yielded a colorless solid, mp 58e60 ꢀC (38.1 mg, 85%). 1H NMR
a yellow oil (87.9 mg, 72%). 1H NMR (400 MHz, CDCl3):
d 8.13 (d,
J¼7.6 Hz,1H), 7.57 (td, J¼7.6,1.3 Hz,1H), 7.42 (t, J¼7.6 Hz,1H), 7.29 (d,
J¼7.6 Hz, 1H), 6.92 (d, J¼3.4 Hz, 1H), 6.64 (d, J¼3.4 Hz, 1H), 5.72 (dd,
J¼10.6, 3.6 Hz, 1H), 3.43 (dd, J¼16.3, 10.6 Hz, 1H), 3.28 (dd, J¼16.3,
(400 MHz, CDCl3):
d
8.16 (d, J¼7.5 Hz,1H), 7.57 (td, J¼7.5, 1.3 Hz,1H),
3.6 Hz, 1H), 2.47 (s, 3H) ppm. 13C NMR (100 MHz, CDCl3):
d 164.9,
7.51e7.34 (m, 6H), 7.29 (d, J¼7.5 Hz, 1H), 5.57 (dd, J¼12.0, 3.1 Hz,
1H), 3.35 (dd, J¼16.4, 12.0 Hz, 1H), 3.14 (dd, J¼16.4, 3.1 Hz, 1H) ppm.
141.1, 138.7, 138.6, 134.0, 130.6, 128.1, 127.6, 126.4, 124.9, 75.9, 35.2,
15.5 ppm. HRMSeESI [MþNa]þ: 267.0448, C14H12O2NaS requires
267.0456.
13C NMR (100 MHz, CDCl3):
d 165.4, 139.1, 138.7, 134.0, 130.6, 128.9,
128.8,128.0,127.5, 126.3,125.3, 80.1, 35.8 ppm. HRMSeESI [MþH]þ:
225.0918, C15H13O2 requires 225.0916.
4.43. 3-Butylisochroman-1-one, 8e30
4.40. 3-(3,4-Dimethoxyphenyl)isochroman-1-one, 8b29
A solution of 2-((trimethylsilyl)methyl)benzoic acid, 3b (104 mg,
ꢀ
0.50 mmol), valeraldehyde (27
m
L, 0.25 mmol), and 4 A MS (100 mg)
A solution of 2-((trimethylsilyl)methyl)benzoic acid, 3b (104 mg,
in anhydrous DMF (2.0 mL) was treated with CsF (152.0 mg,
1.0 mmol) under N2 and the resulting solution was stirred at 80 ꢀC
for 6 h. The reaction mixture was cooled to rt, 2 M HCl (20 mL) was
added and stirred for another 1 h. The residue was extracted with
ethyl acetate (20ꢂ3 mL). Organic layer was washed with water
(2ꢂ10 mL), brine (10 mL), dried over sodium sulfate, and concen-
trated to dryness. Purification by silica gel chromatography eluting
with cyclohexane/ethyl acetate (90:10) yielded a colorless oil
0.50 mmol) and 3,4-trimethoxybenzaldehyde (99.6 mg,
ꢀ
0.60 mmol), and 4 A MS (100 mg) in anhydrous DMF (2.0 mL) was
treated with CsF (152.0 mg, 1.0 mmol) under N2 and the resulting
solution was stirred at 80 ꢀC for 6 h. The reaction mixture was
cooled to rt, 2 M HCl (20 mL) was added and stirred for another
30 min. The residue was extracted with ethyl acetate (20ꢂ3 mL),
the organic layer washed with water (2ꢂ10 mL), brine (10 mL),
dried over sodium sulfate, and concentrated to dryness. Purification
by silica gel chromatography eluting with cyclohexane/ethyl ace-
tate (80:20) yielded a colorless solid, mp 68e70 ꢀC (109.4 mg, 77%).
(34.7 mg, 68%). 1H NMR (400 MHz, CDCl3):
d
8.08 (d, J¼7.6 Hz, 1H),
7.52 (td, J¼7.6, 1.2 Hz, 1H), 7.37 (t, J¼7.6 Hz, 1H), 7.23 (d, J¼7.6 Hz,
1H), 4.56e4.47 (m, 1H), 3.02e2.86 (m, 2H), 1.94e1.83 (m, 1H),
1H NMR (400 MHz, CDCl3):
1.3 Hz, 1H), 7.43 (t, J¼7.5 Hz, 1H), 7.29 (d, J¼7.5 Hz, 1H), 7.04 (d,
d
8.15 (d, J¼7.5 Hz, 1H), 7.57 (td, J¼7.5,
1.77e1.67 (m, 1H), 1.63e1.31 (m, 4H), 0.93 (t, J¼7.2 Hz, 3H) ppm. 13
C
NMR (100 MHz, CDCl3):
d 165.8, 139.4, 133.7, 130.4, 127.7, 127.5,